This invention is generally directed to liquid developer compositions and, more specifically, the present invention relates to liquid developers containing copolymers of an alkene and unsaturated acid derivatives, such as acrylic acid and methacrylic acid derivatives containing pendant fluoroalkyl or pendant fluoroaryl groups, and which copolymers enable liquid inks or developers with high quality imaging. More specifically, the present invention relates to negatively charged liquid developers comprised of a suitable carrier liquid and as a charge adjuvant, and copolymers comprised of alkylene, such as those with from 1 to about 25 carbon atoms such as ethylene and methacrylic acid esters with the ester groups having pendant fluoroalkyl groups such as trifluoroethyl methacrylate, and the like, covalently bonded thereto. Moreover, the copolymers of the instant invention enable tailored small particle size developer designs, prints with high optical clarity, low toner mass imaging, excellent release and transfer of images from intermediate, low temperature fusing and acceptable desirable fixing of the developed images to a receiver, and acceptable image permanence with reduced paper curl.
The developers of the present invention can be selected for a number of known imaging systems, such as xerographic imaging and printing processes, wherein latent images are rendered visible with the liquid developers illustrated herein. The image quality, solid area coverage and image resolution for developed images usually require, for example, sufficient toner particle electrophoretic mobility. The mobility for effective image development is primarily dependent on the imaging system used, and this electrophoretic mobility is directly proportional to the charge on the toner particles and inversely proportional to the viscosity of the liquid developer fluid. For example, an about 10 to 30 percent change in fluid viscosity caused for instance by an about 5.degree. to 15.degree. C. decrease in temperature could result in a decrease in image quality, poor, or unacceptable image development, and undesirable background development, for example, because of a 5 percent to 23 percent decrease in electrophoretic mobility. Insufficient particle charge can also result in poor, or no transfer of the toner to paper or other substrates. Poor transfer, for example, can result in poor solid area coverage if insufficient toner is transferred to the final substrate and can also result in image defects such as smearing and hollowed fine features. To overcome or minimize such problems, the liquid toners of the present invention were arrived at after extensive research efforts, and which toners result in, for example, sufficient particle charge, generally corresponding to an ESA mobility equal to or greater than -2.0 E-10 m.sup.2 /Vs for excellent transfer and maintaining the mobility within the desired range of the particular imaging system employed. Advantages associated with the present invention include improvements in the desired negative charge on the developer particles; in some instances the improvement, as measured by ESA mobility, is from -2.17 E-10 m.sup.2 /Vs without the copolymers of ethylene and methacrylic acid esters with the ester groups having pendant trifluoroethyl groups to -6.60 E-10 m.sup.2 /Vs when the copolymers of ethylene and methacrylic acid esters with the ester groups having pendant trifluoroethyl groups of the present invention are selected. Moreover, small particle developer can be made such that the average area of the particles can be tailored between 1.22 and 0.355 microns (as determined using a Horiba CAPA 500 centrifugal particle analyzer) by control of the number of pendant fluoroalkyl groups on the copolymers of the instant invention of between 0 and 3.5 mol percent. The greater toner charge and smaller particle size developer results in, for example, improved image development and higher quality images, such as higher resolution with less background deposits.
A latent electrostatic image can be developed with toner particles dispersed in an insulating nonpolar liquid. These dispersed materials are known as liquid toners or liquid developers. A latent electrostatic image may be generated by providing a photoconductive layer with a uniform electrostatic charge and subsequently discharging the electrostatic charge by exposing it to a modulated beam of radiant energy. Other methods are also known for forming latent electrostatic images such as, for example, providing a carrier with a dielectric surface and transferring a preformed electrostatic charge to the surface. After the latent image has been formed, the image is developed by colored toner particles dispersed in a nonpolar liquid. The image may then be transferred to a receiver sheet. Also known are ionographic imaging systems.
Typical liquid developers can comprise a thermoplastic resin and a dispersant nonpolar liquid. Generally, a suitable colorant, such as a dye or pigment, is also present in the developer. The colored toner particles are dispersed in a nonpolar liquid which generally has a high volume resistivity in excess of 10.sup.9 ohm-centimeters, a low dielectric constant, for example below 3.0, and a high vapor pressure. Generally, the toner particles are less than 10 .mu.m (microns) average by area size as measured with the Horiba CAPA 500 Particle Sizer.
Since the formation of proper images depends primarily on the difference of the charge between the toner particles in the liquid developer and the latent electrostatic image to be developed, it is desirable to add a charge director compound and charge adjuvants which increase the magnitude of the charge, such as polyhydroxy compounds, amino alcohols, polybutylene succinimide compounds, aromatic hydrocarbons, metallic soaps, and the like, to the liquid developer comprising the thermoplastic resin, the nonpolar liquid and the colorant. A charge director can be of importance in controlling the charging properties of the toner to enable excellent quality images.
In U.S. Pat. No. 5,035,972, the disclosure of which is totally incorporated herein by reference, there are illustrated liquid developers with quaternized ammonium AB diblock copolymer charge directors, and wherein the nitrogen in the ionic A block is quaternized with an alkylating agent.
U.S. Pat. No. 5,019,477, the disclosure of which is hereby totally incorporated by reference, discloses a liquid electrostatic developer comprising a nonpolar liquid, thermoplastic resin particles, and a charge director. The ionic or zwitterionic charge directors may include both negative charge directors such as lecithin, oil-soluble petroleum sulfonate and alkyl succinimide, and positive charge directors such as cobalt and iron naphthenates. The thermoplastic resin particles can comprise a mixture of (1) a polyethylene homopolymer or a copolymer of (i) polyethylene and (ii) acrylic acid, methacrylic acid or alkyl esters thereof, wherein (ii) comprises 0.1 to 20 weight percent of the copolymer; and (2) a random copolymer of (iii) selected from the group consisting of vinyl toluene and styrene, and (iv) selected from the group consisting of butadiene and acrylate. As the copolymer of polyethylene and methacrylic acid or methacrylic acid alkyl esters, NUCREL.RTM. may be selected.
U.S. Pat. No. 5,030,535 discloses a liquid developer composition comprising a liquid vehicle, a charge control additive and toner particles. The toner particles may contain pigment particles and a resin selected from the group consisting of polyolefins, halogenated polyolefins and mixtures thereof. The liquid developers are prepared by first dissolving the polymer resin in a liquid vehicle by heating at temperatures of from about 80.degree. C. to 120.degree. C., adding pigment to the hot polymer solution and attriting the mixture, and then cooling the mixture so that the polymer becomes insoluble in the liquid vehicle, thus forming an insoluble resin layer around the pigment particles.
U.S. Pat. No. 5,026,621 discloses a toner for electrophotography which comprises as main components a coloring component and a binder resin which is a block copolymer comprising a functional segment (A) consisting of at least one of a fluoroalkylacryl ester block unit or a fluoroalkyl methacryl ester block unit, and a compatible segment (B) consisting of a fluorine-free vinyl or olefin monomer block unit. The functional segment of block copolymer is oriented to the surface of the block polymer and the compatible segment thereof is oriented to be compatible with other resins and a coloring agent contained in the toner so that the toner is provided with both liquid-repelling and solvent-soluble properties.
In U.S. Pat. No. 4,707,429 there are illustrated, for example, liquid developers with an aluminum stearate charge adjuvant. Liquid developers with charge directors are illustrated in U.S. Pat. No. 5,045,425. Also, stain elimination in consecutive colored liquid toners is illustrated in U.S. Pat. No. 5,069,995.
In copending patent application U.S. Ser. No. 986,316, the disclosure of which is totally incorporated herein by reference, there is illustrated a process for forming images which comprises (a) generating an electrostatic latent image; (b) contacting the latent image with a developer comprising a colorant and a substantial amount of a vehicle with a melting point of at least about 25.degree. C., which developer has a melting point of at least about 25.degree. C., and wherein the contact occurs while the developer is maintained at a temperature at or above its melting point, said developer having a viscosity of no more than about 500 centipoise and a resistivity of no less than about 10.sup.8 ohm-cm at the temperature maintained while the developer is in contact with the latent image; and (c) cooling the developed image to a temperature below its melting point subsequent to development.
In U.S. Pat. Nos. 5,306,591 and 5,308,731, the disclosures of which are totally incorporated herein by reference, there is illustrated a liquid developer comprised of thermoplastic resin particles, a charge director, and a charge adjuvant comprised of an imine bisquinone; and a liquid developer comprised of a liquid, thermoplastic resin particles, a nonpolar liquid soluble charge director, and a charge adjuvant comprised of a metal hydroxycarboxylic acid, respectively.
In copending patent application U.S. Ser. No. 065,414, the disclosure of which is totally incorporated herein by reference, there is illustrated a liquid developer comprised of thermoplastic resin particles, and a charge director comprised of an ammonium AB diblock copolymer of the formula ##STR1## wherein X-- is a conjugate base or anion of a strong acid; R is hydrogen or alkyl; R' is alkyl; R" is an alkyl group containing from about 6 to about 20 carbon atoms; and y and x represent the number average degree of polymerization (DP) wherein the ratio of y to x is in the range of from about 10 to 2 to about 100 to 20. The charge adjuvants and other appropriate components of these copending applications may be selected for the liquid toners of the present invention.
In copending patent application U.S. Ser. No. 200,988, filed Feb. 24, 1994, the disclosure of which is totally incorporated herein by reference, there is illustrated a liquid developer comprised of thermoplastic resin particles, a charge director, and a charge adjuvant comprised of an alkene and unsaturated acid derivatives, such as acrylic acid and methacrylic acid derivatives, containing pendant ammonium groups and which copolymers function as positive charge adjuvants. More specifically, the copending application relates to positively charged liquid developers comprised of a suitable carrier liquid and a charge adjuvant comprised of copolymers of alkylene, such as those with from 1 to about 25 carbon atoms such as ethylene and methacrylic acid esters with the ester groups having pendant ammonium groups such as N,N,N-trimethylammonium bromide, N,N-dimethylamine hydrogen bromide, N,N,N-trimethylammonium tosylate (p-toluenesulfonate), N,N-dimethylamine hydrogen tosylate, N,N,-dimethylamine hydrogen dinonylnaphathalene sulfonate, and the like covalently bonded thereto.